JPS62131253A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a heatdevelopable color photosensitive material having superior preservation stability and giving a high density image with a high S/N by using a specified compound as the precursor of a developing agent. CONSTITUTION:The heatdevelopable color photosensitive material having photosensitive silver halide, a coupler bonding to the oxide of a developing agent, a hydrophilic binder and at least one kind of compound represented by the formula as the precursor of the developing agent on the support is heated in the presence of a base or a base generator. The used amount (mole) of the precursor is 0.1-10 times, preferably 0.2-3 times the total amount of silver coated to form the photosensitive layer. The base or the base generator may be previously incorporated into the photosensitive material or may be supplied from the outside at the time of the heatdevelopment. In the formula, each of R1-R4 is H, halogen or the like and A is hydroxyl, a group giving hydroxyl by the action of a nucleophilic reagent or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming method. This invention relates to an image-forming method in which a developing color light-sensitive material is heated in the presence of a base or a base generator.

(Prior art) Compared to other photographic methods such as electrophotography and diazo photography, silver halide photography has been the most popular method since it has superior photographic properties such as sensitivity and gradation adjustment. It has been widely used. In recent years, a technology has been developed that uses silver halide to form images on light-sensitive materials by changing from the conventional wet processing using a developing solution to a dry processing using heating, etc., which allows images to be obtained easily and quickly. San came.

Heat-developable photosensitive materials are known in the art, and a description of heat-developable photosensitive materials and processes thereof is disclosed in U.S. Pat. No. 4,152.
．． No. 904, No. 501.678, No. 392.02
No. 0, No. 457.075, British Patent No. 1.131.
No. 10 f3, No. 1.167.777, and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-17029).

Many methods have been proposed for obtaining color images. Regarding the method of forming a color image by combining a completed developer with a coupler, please refer to the US Pat. 4551
．． No. 286, p-phenylene diamine reducing agents and phenolic or active methylene couplers are disclosed in U.S. Pat.
In Belgian Patent No. 802.519 and in Research Disclosure, September 1975, p. 31.32, P-aminophenol reducing agents were introduced in the United States!
FiRa, No. 21,2 io proposes a combination of a sulfonamidophenol reducing agent and a four-layer coupler.

(Problems to be Solved by the Invention) Japanese Patent Laid-Open No. 58-79.247 describes a method for releasing a diffusible dye by combining an oxidized developer and a coupler.
It is stated in the number etc. However, the developing agents used in these known heat-developable color light-sensitive materials, such as p-phenylene diamines and p-amine phenols, have poor storage stability and cause significant coloring to the background. Furthermore, although p-sulfonamide phenols improve storage stability, they have poor silver developability and coupling properties, and high-density images cannot be obtained.

Furthermore, the hydrazone derivatives described in Research Disclosure Magazine, June 1980, No. 19417 have poor coupling properties, and only IJ images can be obtained at low ##. On the other hand, the sulfamate salts described in JP-A-56-14-135, the urea derivatives described in U.S. Pat. No. 4,426.441, the urea derivatives described in JP-A-59-5-851, etc. -phenylene diamines or HP-amine phenols are stabilized with a protective group, but both have poor silver developability and can only provide images with a low @ degree.

In view of this, the first object of the present invention is to provide a heat-developable color photosensitive material that has excellent storage stability and provides a cylindrical image with high density and S/N ratio, and a 7i method for forming the image. The second objective is to provide a developer precursor for a heat-developable color light-sensitive material that exhibits stability over time, silver developability, and compulsivity.

(Means for Solving the Problems) For the purpose of the present invention, at least a photosensitive silver halide, an oxidized form of a developer and a coupler, a hydrophilic binder, and a developer precursor as shown below are prepared on a support. This can be achieved by an image forming method in which a heat-developable color photosensitive material containing at least one compound represented by the formula [Z] is heated in the presence of a salt and a base generator to a temperature of 15 cm. .

R3R.

[In the formula, R1, Rt, R, and R4 are independently hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, cycloalkyl groups, aralkyl brackets, hydroxyl groups, amino groups, substituted amino groups, alkoxy groups, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryl group, carbamoyl group, substituted carbamoyl group, sulfamoyl, S, 119 sulfamoyl group, acyl group, acyloxy group or alkoxycarbonyl group, and R1 and R2 represent R3 and R4 may be linked to form a base.

A represents a hydroxyl group, an alkyl, alkenyl, cycloalkyl, or aralkyl group that forms a hydroxyl group, unsubstituted or substituted, by the action of a nucleophilic reagent, and R6 and Rγ may be linked to form a heterocycle. ).

The - group or the inner group of hi (Rs and Rγ) may be connected to form a complex. Cyano group′ in RS! A detailed explanation of the present invention will be given below on e-b-t-0 regarding the alkylsulfonyl group and arylsulfonyl group having unsubstituted or substituted groups at fc.

General formula [Z 3 vc and R, %R1, R:l and 1(.

independently hydrogen atoms, halogen atoms (e.g. chlorine atoms,
a bromine atom, a fluorine atom), an alkyl group (preferably an alkyl group having 1 to 32 carbon atoms, such as a notel group, an ether group,
butyl group, octyl group), alkenyl group (preferably alkenyl group having 2 to 32 carbon atoms, such as allyl group, vinyl group, crotyl group, etc.), cycloalkyl group (preferably cycloalkyl group having 3 to 8 carbon atoms) groups, such as cyclohexyl groups, cyclobentel groups, etc.], aralkyl groups (preferably aralkyl groups having 7 to 18 carbon atoms, such as benzyl groups,
β-phenethyl group, etc.), hydroxyl group, amino group, substituted amino group, alkoxy group (preferably 1 to 62 carbon atoms)
Alcoquine group, methoxy group, ethoxy group, benzyloxy group, acylamino group (preferably carbon number 2)
-32 acylamino groups, such as acetylamino groups, butyrylamino groups, hexanoylamino groups, stearoylamino groups, etc.), alkylsulfonylamino groups (preferably alkylsulfonylamino groups having 1 to 32 carbon atoms, such as methylsulfonylamino groups, propylsulfonylamino group, etc.), arylsulfonylamino group (preferably an arylsulfonylamino group having 6 to 18 carbon atoms, e.g. evaphenylsulfonylamino M, p-chlorophenylsulfonylamino group), aryl group (e.g. phenyl group, naphthyl group, etc.) ], carbamoyl group, substituted carbamoyl group,
Sulfamoyl group, substituted sulfamoyl group, acyl group (
Preferably an acyl group having 2 to 32 carbon atoms, such as an acetyl group, a butyroyl group, an impteroyl group, etc.), an acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, 1
+1" (acyloxy group, benzoyloxy group, etc.),
or an alkoxycarbonyl group (preferably 2 to 2 carbon atoms)
R1 and R
1 or R3 and R4 may be connected to form a ring (for example, a saturated ring formed by a trimethylene group, a tetramethylene group, etc., a naphthalene ring formed by a penzologue, etc.).

When R,, Rt, R3 or R4 is an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or a group containing an aliphatic hydrocarbon group such as an aralkyl group, an alkoxy group or an acylamino group, these aliphatic Group hydrocarbon system 4 may be linear or branched. When R1 to R4 are substituents other than a hydrogen atom, a halogen atom, or a hydroxyl group,
These are allowed for R17i to R4, which will be described later.
It may have one or more substituent groups (including substituted atoms; the same applies hereinafter), and when two or more groups exist, they may be the same or different.

Permissible substituents for R1 to R4 include aliphatic groups, aryl groups, heterofilling, aliphatic oxy groups, aromatic oxygen groups, acyl groups, ester groups, amide groups, imido groups,
Examples include an aliphatic sulfonyl group, an arylsulfonyl group, a heterosulfonyl group, an aliphatic thio group, an arylthio group, a heterothio group, a hydroxyl group, a cyano group, a carboxyl group, a sulfo group, and a nitro group.

When R1 to R4 are a substituted amino group, a substituted carbamoyl group, or an if-substituted sulfamoyl group, the permissible substituents have the same meanings as the substituents allowed for R1 to R4 above.

In the case of a hydroxyl group precursor, it is a group that provides a hydroxyl group by the action of a nucleophile. Here, the nucleophile is 0H-
Examples include anionic reagents such as 1OR-1s o31-, and compounds having lone pairs of electrons such as primary or secondary amines, hydrazines, hydroxylamines, alcohols, and thiols.

Precursors of hydroacetic acid groups include, for example, acyloxy7 groups (preferably 1 to 18 carbon atoms, such as acetyloxy groups, trifluoroacetyloxy groups, penzoyloxy groups, etc.),
Alkylsulfonyloxy group (preferably 1 to 8 carbon atoms)
, for example, methanesulfonyloxy group%), arylsulfonyloxy group (preferably 6 to 18 carbon atoms, e.g. phenylsulfonyloxy group -t, , p-chlorophenylsulfonyloxy M, etc.), alkoxycarbonyloxy group (preferably carbon number 2 = 18, for example, nodoxycarbonyloxy group, etc.), aryloxycarbonyloxy group (
Good! L<Irl carbon number 7-18, e.g. hafenoxycarbonyloxy group, etc.), dialkylphosphoryloxy group (preferably carbon number 2-12, e.g. diethylphosphorylox 7 groups, etc.), diarylphosphoryloxy group (preferably has 12 to 24 carbon atoms, such as diphenylphosphoryloxy group), and the like.

Hydrogen atom, substituted or unsubstituted alkyl group (preferably 1 to 32 carbon atoms, such as ethyl group, methanesulfonylamine ethyl group, hydroxyethyl group, etc.), substituted or unsubstituted alkenyl group (preferably (preferably 3 to 18 carbon atoms, such as allyl group), gt or unsubstituted cycloalkyl group (preferably 3 to 12 carbon atoms, such as cyclohexyl group)
, Mano represents a substituted or unsubstituted aralkyl group (preferably 7 to 18 carbon atoms, flJi represents a benzyl group, β-phenethyl group, etc.), and R6 and R7 are connected to form a heterocyclic ring (for example, a pyrrolidine ring, piperidine ring, etc.). A ring, a morpholine ring, etc. may be formed.Also, (Rz and Rs) and (Rs
and Ry ) or both groups may be linked to form a heterocycle (eg, tetrahydroquinoline ring, julolidine ring, etc.).

Rsμ cyano group, unsubstituted or substituted alkylsulfonyl group (preferably 1 to 18 carbon atoms, e.g. methanesulfonyl group, octylsulfonyl group, etc.), or unsubstituted or arylsulfonyl group having 1 substituent group (preferably carbon number 6 to 1a, PI, p-phenylsulfonyl group, p-chlorophenylsulfonyl group, 2.5
-dichlorophenylsulfonyl group, 44-dichlorophenylsulfonyl group, 2.4-cyanophenylsulfonyl group, m-nitrophenylsulfonyl group, p-)f-ruphenylsulfonyl group, p-cyanophenylsulfonyl group, α-naphthylsulfonyl group , β-naphthylsulfonyl group, m-methanesulfonylphenylsulfonyl group, p
-methoxyphenylsulfonyl group, etc.).

Preferred examples of R1, R8, R3, and R4 include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an aryl group, a carbamoyl group, a substituted carbamoyl group, etc. n/). A (2) Preferred examples include hydroxyl group, acylox7 group, alkylsulfonyloxy group, arylsulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, dialkylphosphoryloxy group, diarylphosphoryloxy group, dialkyl group. Examples include amino group (which may be substituted with an alkyl group), pyrrolidino group, piperidino group, morpholino group, etc. Preferred examples of R5 include thefomethanesulfonyl group, benzenesulfonyl group, p- Examples include chlorophenylsulfonyl group, 2.5-dichlorophenylsulfonyl group, m-nitrophenylsulfonyl group, 1-naphthalenesulfonyl group, and cyan group.

Preferred specific examples of the developer precursor having the general formula (ZJ) are shown below, but the present invention does not apply to these KISI-defined nib.

0,'- ct Br Br ct atbr
01T CT N3 CT CT CT CT CT CT NHCOC, 7N3 ゜ CT BR CLT CH3 methods used in the present invention, for example, β -replacement ethanol and phenyl isocyanite added. It can be synthesized by a reaction or a condensation reaction of β-substituted ethanols and urethanes. Specific synthesis examples of the developer precursor used in the present invention are shown below.

Synthesis Example (Synthesis of Exemplified Compound 1) 15.7 F of phenyl chloroformate was added dropwise to a mixture of 35.62 d of 2.6-dichloro-4-aminephenol and 400 d of acetonitrile at room temperature.

After stirring for one hour at room temperature, the precipitated crystals were collected from door to door. F
Concentrate the solution under reduced pressure to about half the volume, then add 3N
2oo- of hydrochloric acid was added, and all of the precipitated fc crystals were taken and washed with water.

Above crystal 14. qr to β-phenylsulfonylethanol 1a6? 130t under reduced pressure of 10 wag.
It was heated to l:. 1 while distilling off the generated phenol.
The mixture was heated and stirred at 30°C for 3 hours. After cooling, he ether 50-
and 50% of n-hexane were added, and the resulting crystals were counted. The obtained @acid was recrystallized from acetonitrile (IJ) to give 9.22% of white crystals of Exemplified Compound 1. Melting point 179-
182℃.

The developer precursors of general formula CZ] used in the present invention may be used alone or in combination of two or more. In general, α can be used in an amount ranging from 1 to 10 times the mole of the entire coated silver layer constituting the photosensitive layer, preferably (lL2
Double mole or triple mole? To use.

The developer precursors of this invention can be incorporated into the sensitizer in a number of ways. According to a method commonly known as the oil protection method, it may be dissolved in a hydrophobic oil and emulsified and dispersed as an oil-in-water dispersion in water or a hydrophilic colloid solution, or it may be dissolved in a water-miscible medium. The compound may be added as fine particles in water or a hydrophilic colloid solution, or the compound in a solid state may be introduced into water or a hydrophilic binder using a ball mill or the like.

The developer precursor represented by the general formula [Z] used in the present invention may be added to any layer constituting the heat-stable color photosensitive material. For example, a photosensitive halogen Examples include a silver oxide emulsion layer, a hydrophilic colloid layer, and an intermediate layer.

There are 41 types of couplers that are viscous with the oxidized form of the developer. For example, T, )L James Nissho-T
theory of the photog
rapic process-4thEd.
Any of the couplers described in pages 554 to 661 and pages 284 to 295 of 1 Photo Chemistry by Makoto Kikuchi, 4th edition (Benmuro Publishing) can be used in the present invention.

In the present invention, both 4-equivalent couplers, in which the moiety that binds to the oxidized form of the developer is a hydrogen atom, and 2-equivalent couplers, in which the moiety is substituted with a leaving group, can be used.

In addition, both so-called fiber-dispersed couplers, which have both edges of a hydrophilic group and a hydrophobic diffusion-resistant group in the coupler, and oil-protected dispersion-type couplers, which have only hydrophobic diffusion-resistant groups, can be used.

Some of the couplers having diffusion-resistant groups include those disclosed in JP-A-58-14
Coupler having a hydrophobic ballast group in the leaving group described in JP-A-58-149, No. 047, etc.; Coupler having a leaving group linked to the polymer main chain as described in JP-A-58-149, 047; U.S. Patent No. Mu37a952: A451,820: 4,0
80.211; 4,215°195; 4.409
．． 320, etc., are included. Also, British Patent No. 1.330゜524;
No. 9.165; JP-A-57-186.744; 57
-207.250; 58-79.247, and the like, colored cufflers containing a dye component in the leaving group are also useful in the present invention.

Couplers preferably used in the present invention include active methylene and active methine compounds, phenols, naphthols, pyrazoles and condensed pyrazole compounds, and particularly preferred are the following general formulas (13% formula %, RH, Rg, RIO, R11rLj each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acylamino group, an alkoxyalkyl group, From aryloxyalkyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl i, am sulfamoyl group, alkylamino group, arylamino group, acyloxy group, acyloxyalkyl group, tIL-substituted ureido group, cyano group, Enoshima residue The selected substituents are further added to these substituents, including an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a 77 group, a nitro group, a carbamoyl group, and a 1! , a sulfamoyl group, a fit-substituted sulfamoyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, an aryloxy group, an aralkyl group, or an acyl group. Leaving group? Represents a halogen atom, anroxy group, sulfonylokyne group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyloxy group, dialkylcarbamoyloxy7 group, imide group, N-multifunctional ring residue, A typical example of a coupling-off group is a pyridinium group.
R9% It is preferable that any one of R1°, R11, and frame x1 is a ballast group that provides diffusion resistance, and these groups may be linked to the polymer main chain.

Diffusion-resistant compounds (dye-releasing cabranos) that undergo a coupling reaction with an oxidized developer to release a diffusible dye (dye-releasing cabranos) can also be used in the present invention. For example, the compound represented by the following formula (9) is also a snake.

0oup -Link -Dye (%l
) Narita, 0oup represents a coupler residue that is camped with the oxidized form of the developer, and preferably represents a portion obtained by removing XI from the coupler represented by the general formula (4) above.

Link is bonded to the active site of the Coup portion, and when performing a coupling reaction with the dye-releasing coupler represented by the above formula (to) or the oxidized form of the developer, the bond between it and the Coup portion is cleaved. For example, azo group, azoxy group, -0-, -)1g-, alkylidene group, -8-
1-S-S-1-NH8O! In addition to groups such as -, the coupling-off group Xl described above is also useful.

Dye represents a dye or dye precursor.

Preferred among the dye-releasing agents represented by the above formula (to) are those in which the rz coup is a phenol-type blade residue, a naphthol coupler residue, or an indanone-type coupler residue, and the link is an oxygen atom or C in perfect elementary atom
3 oup.

In the present invention, the coupler is U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in the above. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, 7-tar acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, )'J phenyl phosphate, tricresyl phosphate, dioctyl buter phosphate], citric acid esters (flJ eha acetyl citrate tripterno, benzoic acid esters (octyl benzoate), alkyl amides (e.g. diethyl lauryl amide) , fatty acid esters (e.g. dibutoxyethylsac7)
ate, dioctyl azelate), torinohptaphosphates (e.g., high boiling point organic solvents such as trimene tripterno, or low boiling point organic solvents with a boiling point of about SaC to 160°C, such as lower alkyl acetate, butyl acetate, etc.) It is dissolved in acetate, ethyl propionate, secondary butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, metelcerone rub acetate, cyclohexanone, etc., and then dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Mafc% Publication No. 51-39853, Japanese Unexamined Patent Publication No. 51-599
The dispersion method using a polymer described in No. 45 can also be used. Furthermore, when dispersing couplers in hydrophilic colloids, various surfactants can be used, and examples of these surfactants include Nos. (37) to 157636 of JP-A-59-157.
Those listed as surface active 41 on page (58) can be used.

The amount of high-boiling organic solvent used in the present invention is 101 or less, preferably 52 or less relative to the coupler 11 used.

In the present invention, a reducing substance may be used in combination with the photosensitive material. Examples of reducing substances include auxiliary developers that can be used in combination with the developer precursor of the present invention. The auxiliary developer may be diffusible or non-diffusible.

Useful auxiliary developers include hydroquinone, t-butylhydroquinone, alkyl f-substituted hydroquinones such as 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and methoxyhydroquinone. There are alkoxy-substituted hydroquinones and polyhydroquine benzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N-di(2-ethoxyether)hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1 Pyrazolidones such as -7 Uni-3-pyrazolidone, reductones, and hydroxyctetronic acids are useful.

It can be used as an auxiliary developer within a certain concentration range. A useful concentration range is (10005 times molar to 10 times molar) with respect to the total amount of silver coated, and a particularly effective concentration range is ij, [1
001 times mole to 15 times mole.

Various types of base generators are known for use in the present invention. It is a compound that can activate development by making the system basic as a base generator, or a compound that has nucleophilic properties, and is extremely effective in increasing the maximum density. Particularly in the present invention, since the compound represented by the general formula [z] is a precursor of a developer, a base is essential during heat development in order to remove the protective group from this precursor and develop development activity. That is, in the image forming method of the present invention, a photosensitive material is heat-developed in the presence of a base or a base or a base generator. Specifically, a base or a base generator may be added to the photosensitive material in advance, or may be supplied from the outside during heat development (for example, it may be supplied dissolved in water). The base generator includes a base breaker and those used in the base generation system described below, such as those that generate a base by reacting with other compounds.

When added to the photosensitive material layer, it is advantageous to use a base precursor, for example, to generate a base.

The base precursor referred to here is one that releases a base upon heating. Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates: ammonium water; Oxide: 4
Hydroxides of alkylammoniums include hydroxides of other metals, organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines), aromatic amines. (N-alkyl f
l-substituted aromatic amines, N-hydroxyklylalkoxy-substituted aromatic amines and bis[p-(dialkylamine)phenyl]methanes], cypress amines, amidines,
Examples include cyclic amidines, guanidines, and cyclic guanidines, and U.S. Pat. Organic compounds containing amino acids such as 6-aminocaproic acid are useful. In the present invention, those having a pKa value of 8 or more are particularly useful.

Examples of base breakers include salts of organic acids and bases that decompose by decarboxylation when heated, compounds that decompose through Rossen rearrangement, Beckmann rearrangement, etc. and release amines, and other compounds that cause some kind of reaction when heated and release bases. Don't use what you do.

Preferred base breakers include the organic base breakers mentioned above. For example, salts with thermally decomposable organic acids such as trichloroacetic acid, trifluoroacetic acid, globiol number, cyanacetic acid, sulfonylacetic acid, acetoacetic acid, etc., US Pat. Examples include salts with 2-carboxycarboxamide described in QBa496.

Preferred specific examples of base breaker are shown below. Examples of compounds that are thought to decarboxylate the acid moiety and release a base include the following.

Examples of trichloroacetic acid derivatives include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, and 2-picoline trichloroacetic acid.

Other British Patent No. 99a945, US Patent No. &22G
, No. 846, Japanese Unexamined Patent Publication No. 50-2λ625, etc., using the base breaker.

For substances other than trichloroacetic acid, US% 4. l
]B&496, 2-carboxylic sulfoxamide-derived conjugate 2, described in U.S. Pat. No. 4,06 [1L420, described)
α-sulfonia acetate N conductor, JP-A-59-1AOS
Examples include phenylpropiolic acid derivatives described in No. a9, and salts of gropiolic acid derivatives and bases described in JP-A-59-180537. As the base component, in addition to organic bases, alkali metals and alkaline earth metals are also effective and are described in JP-A-59-195237.

7 lucasors other than those mentioned above include hydroxamic carbamates described in JP-A-59-168440 using Rossen rearrangement, and JP-A-59-15763, which generates nitriles.
Aldoxime carbamates described in No. 7 are effective.

In addition, the amine imides described in Research Disclosure magazine, May 1977, No. 15776, Imakaikai 50-2
The compound described in Japanese Patent No. 2,625, which decomposes at high temperature to produce a base, is preferably used.

A base generating system a in which a base is generated by contacting two substances added to each of the primary light-sensitive material layer and the dye fixing material layer during thermal development is particularly useful in the present invention. Examples of such base-generating Shio 1j include combinations of metal complexing agents and SM metal salts such as calcium, magnenium, aluminum, zinc, and copper.

These bases can be used in a wide range of primary base grecursers. A useful range is not more than 50% by weight of the coated dry film of the photosensitive material, more preferably from α01% by weight to 40% by weight.

Of course, the bases or base precursors described above can be used not only for promoting dye image formation, but also for other purposes, such as adjusting the pHO value.

It can be placed at any appropriate position in the above-mentioned components constituting the bnb photothermographic material used in the present invention. If necessary, one or more of the components can be disposed in one or more film layers in the light-sensitive material. In the case of a protective layer, it is desirable to add specific proportions of reducing agents, image stabilizers and/or other additives as described above to the protective layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
It may be silver chlorobromide, silver chloroiodide, or silver chloroiodobromide.

Specifically, pages 35 to 36 of Japanese Patent Application No. 59-228551.
Page, U.S. Pat. No. 4,500,626, column 50, Research Disclosure, June 1978, 9-1 ()
Any of the silver halide emulsions described in Sada (RD17Q29) and others can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Common sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. for emulsions for conventional light-sensitive materials can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing complex compound (Japanese Patent Application Laid-open Nos. 58-126526 and 5B-215644).
.

The silver halide emulsion used in the present invention may be of the coated surface latent image type in which the latent image is mainly formed on the two surfaces of the grains, or it may be of the internal latent image type in which the latent image is formed inside the grains. It is also possible to use direct inversion emulsions, which are combinations of internal layer image emulsions and nucleating agents.

The photosensitive silver halide coating used in the present invention ranges from n1ai to i097m2.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with a photosensitive compound.

In this case, it is necessary that the photosensitive silver halide and the organic metal salt be in contact with or close to each other and have a distance VC.

Among such organic silver salts, organic silver salts are particularly preferably used.As an organic compound that can be used to form the above-mentioned organic silver salt oxidizing agent, Japanese Patent Application No. 59-228551 page 67~
Page 39, U.S. Pat. No. 4.50 to No. 626, columns 52 to 55
Compounds listed in the columns, etc.

Silver salts of carboxylic acids having an alkynyl group, such as silver phenylgropiolate described in Japanese Patent Application No. 1988-221535, are also useful.

The above organic silver salts can be used together in an amount of α01 to 10 mol, preferably α01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver norogenide and organic silver salt is 50IIg to 10g in terms of silver.
r/m” is excessive.

The silver halogenide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes that may be used include cyanine dyes, melonanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioquinol dyes.

Specifically, JP-A-59-180550 and JP-A No. 60-1
No. 40335, Research Disclosure Magazine 197
June 8 issue 12-13jfit (RD17029J Temple), heat decolorizing sensitizing dyes described in JP-A-60-111259, Japanese Patent Application No. 60-172967, etc. .

These sensitizing dyes may be used alone or in combination, and are often used in combinations of sensitizing dyes, particularly for the purpose of supersensitization.

Along with the sensitizing dye, it also has a spectral sensitizing effect.
The emulsion may contain a dye or a substance that does not substantially absorb visible light and exhibits supersensitization (e.g., U.S. Pat.
No. 510, No. 4615.613, No. 615,641, No. 617, 295, No. 635 to No. 574.
．． The one described in No. 721.

These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as described in U.S. Patent No. 4.18 to 7.
It may be carried out before or after nucleation of silver halide grains according to No. 56 and No. 4.225.666.

The amount added is generally about 10-' to 10-2 mol per mol of silver halide.

In the present invention, an image formation accelerator can be used in the photosensitive material l/ic. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents, promoting reactions such as decomposition of dyes and release of diffusible dyes during production of dyes from dye-donating substances, and It has functions such as promoting the movement of dyes from the photosensitive material layer to the dye fixing layer, and from a physicochemical function, it is effective against bases or base breaker, nucleophilic compounds, high boiling point organic solvents (oil, hot solvents, interfaces, etc.). It is classified into active agents, compounds that interact with silver or silver ions, etc.

However, these groups of substances generally have a certain characteristic, and usually have some of the above-mentioned promoting effects.

Details of these are described in Japanese Patent Application No. 59-21397Q, pages 67 to 71.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The term "development stopper" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the base concentration in the film and stop development after proper development, or a compound that interacts with silver and silver salts to stop development. 11j.

Specifically, acid full cursor 2 releases acid upon heating.
With the base that coexists with heating! Examples include electrophilic compounds, nitrogen-containing heterogeneous compounds, mercapto compounds, and their Ail precursors that cause conversion reactions (for example, Japanese Patent Application No.
No. 216928, No. 59-48305, No. 59-85
No. 834 is the compound described in No. 59-85836).

Compounds that release mercapto compounds upon heating are also useful;
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 59, No. 60-24665, No. 60-29892, and No. 59-176350.

Further, in the present invention, a compound that activates the development and stabilizes the image can be used in the photosensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51-52.

A variety of anticapri agents may be used in the present invention. Antifoggants include anols, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, and mercapto compounds and metal salts thereof as described in JP-A-59-111,636. Acetylene compounds described in Patent Application (B) dated October 14, 1985 (% Applicant: Fuji Photo Film Co., Ltd.) are used.

In the present invention, if necessary, an image toning agent is added to the photosensitive material. It can contain. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92-96.

The binders of the photosensitive material of the present invention can be used alone or in combination. A hydrophilic one can be used as this inder. Hydrophilic binders are typically transparent or translucent hydrophilic binders, such as natural substances such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, polysaccharides such as starch and gum arabic, and polyvinylpyrrolidone. , synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide monomers. Other compounds include dispersed vinyl compounds that are used in latex form to add to the dimensional stability of photographic materials.

In the present invention, the coating amount of the binder is 202 or less per m2, preferably 72 or less, preferably 72 or less.

The ratio of the binder to the high boiling point organic solvent containing a hydrophobic compound such as a dye-donating substance in the binder is less than or equal to the common medium ICC for the binder of 11, preferably 15.
A value of ω or less, more preferably α3CC or less is suitable.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other binder layer.

Specific examples of hardeners include tp! f Application No. 59-268926, page 94 to 95, and JP-A-59-157656
No. 589 (N) or Ligera n, these can be used by assembling them into a single hole.

The photosensitive material in the present invention and optionally used t'
L/) The support used for the dye-fixed forest material is one that can withstand the processing temperatures. Common supports include glass, paper, monolithic films, metals and their analogues;
The supports listed on pages 95 to 96 of Mei IIa No. 6 can be used.

When the light-sensitive material used in the present invention contains a colored dye-donating substance, the light-sensitive material may contain various dyes such as irradiation and yahalation preventive substances. Although it is not necessary to do so, Japanese Patent Application No. 59-268926, pp. 97-98 and U.S. Patent No. 4.
500.626, column 55 (lines 41-52), filter dyes, absorbent substances, etc., can be contained.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan, the R6 photosensitive element used in the present invention contains at least five halogenated layers, each sensitive to a different spectral region. It is necessary to have a silver emulsion layer.

A typical combination of at least five light-sensitive silver halide emulsion layers sensitive to different spectral regions is described in JP-A-59-180550.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials, and layers other than the photosensitive layer, such as anti-glaze layer, 4m, 'm, protective layer, Intermediate layer, AH layer, peeling II! layers, matte layers, etc. As each frame additive, frame, Lisa F. Disclosure magazine June 1978 issue, pages 9 to 15 (RD1
7029), additives described in Japanese Patent Application No. 59-209563, etc., such as plasticizers, dyes for improving sharpness,
Additives include AI (dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents), ultraviolet absorbers, anti-slip agents, antioxidants, and anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Additionally, this protective layer may contain a mordant and a UV absorber. The protective layer and the intermediate layer may each include two or more layers.

In addition, a reducing agent is added to the intermediate layer to prevent color fading and color mixing.
UV absorbers and white pigments such as TiO2 may also be included. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

The photographic element of the present invention comprises a photosensitive element that forms and releases a dye upon heat development and, if necessary, a dye fixing element that fixes the dye.

In particular, a photosensitive element and a dye fixing element are essential in systems that form images by diffusion transfer of dyes, and in a typical form, the photosensitive element and dye fixing element are separately coated on two supports. Coated on the same support as the form n
It is broadly divided into two types.

The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
Regarding the relationship with white reflection I-, the relationships described in Japanese Patent Application No. 59-268926, No. 58-59 Negative, and U.S. Pat.

A typical configuration in which the photosensitive element and the dye fixing element are coated on the same support is one in which there is no need to peel off the photosensitive element from the dye fixing element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent support/photosensitive layer/white reflective layer/dye fixing layer, transparent support/dye fixing element white reflective layer/photosensitive layer, and the like.

Another typical embodiment in which the light-sensitive element and the dye-fixing element are coated on the same support is disclosed in, for example, JP-A-56-67840.
Canadian Patent No. 674.082, U.S. Patent No. 473
As described in No. 0,718, there is a form in which part or all of the photosensitive element is peeled off from the dye fixing element.
Examples include those having a release layer coated at an appropriate position.

The photosensitive element or dye fixing element may be in the form of an electrically conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element can be made using conventionally known techniques for producing a resistance heating element.

As the resistance heating element, there are two methods: one uses a thin film of an inorganic material exhibiting semiconductivity, and the other uses a thin film of an organic material in which conductive fine particles are dispersed in a binder.

For materials that can be used in these methods, patent application No. 59-151
Those described in the specification of No. 815 etc. can be used.

The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided as necessary.

The layer structure of the dye fixing element, the location of the binder, the additive, the mordant addition layer, etc. are described in the specification of % Application No. 59-268926, page 62, line 9 to page 65, line 18, and the following patents cited therein. What is described in the specification is also applicable to this application.

In addition to the J- mentioned above, the dye fixing element used in the present invention can be provided with auxiliary surfaces such as a release layer, a capping agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or a base fluxer to promote dye transfer, a hydrophilic heat solvent, an anti-fading agent to prevent fading of the dye, a UV absorber, and a slip agent. , a capacitor, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, an optical brightener, etc. may be included.

Specific examples of these additives are described on pages 101 to 120 of Japanese Patent Application No. 59-209565. b0 The binder in the above layer is preferably hydrophilic, and a transparent or translucent hydrophilic colloid is used. is typical. In a specific example, a fast binder is used in the photosensitive material mentioned above.

The image receiving layer in the present invention is a dye fixing layer used in a heat-developable color light-sensitive material, and any mordant C that is commonly used can be used as the image receiving layer, but polymer mordants are particularly preferred. Here, examples of the polymer mordant include a polymer containing an amino group, a polymer containing a nitrogen-containing complex #J, and a polymer containing a quaternary cation group.

Regarding this specific example, please refer to % Application No. 59-268926 98
-pages 100 and 57-6 of U.S. Patent No. 4.500626
It is not written in column 0.

In the present invention, the coating method for the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, pack layer, and other layers is disclosed in U.S. Patent No. 4.500.
The method described in columns 55 and 56 of No. 626 can be applied.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used,
For example, the light source described on page 100 of Japanese Patent Application No. 59-268926 and column 56 of US Pat. No. 4,500,626 can be used.

The heating temperature in the heat development step is about 0°C to about 250°C, but it is particularly useful to set the heating temperature to about 0°C to about 180°C. Transfer is possible at a temperature ranging from room temperature to room temperature, but it is particularly preferable to transfer at a temperature of 50° C. or higher and about 10° C. lower than the temperature in the heat development step.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc. can be used.

Also, Japanese Patent Application Publication No. 59-218445, Japanese Patent Application No. 60-79
As detailed in No. 709, etc., a method in which development and transfer are performed simultaneously or successively by heating in the presence of a small amount of a solvent such as water may also be useful. In this method, the image formation accelerator mentioned above is either a dye fixing material or a photosensitive material! It may be included in both of them in advance, or it may be supplied from the outside.

In the above-mentioned system in which development and transfer are carried out simultaneously or continuously, the heating temperature is preferably 50° C. or higher and below the boiling point of the solvent; for example, when the solvent is water, it is preferably 50° C. or higher and 100° C. or lower.

Further, a solvent may be used to transfer the mobile dye to the dye fixed layer.

Examples of solvents used to accelerate development and/or to transfer mobile dyes to the fixed dye layer include water and basic aqueous solutions containing RI-free alkali metal salts and organic bases.
As these bases, those described in item 0 of the image formation accelerator can be used. Further, a low boiling point solvent, or a mixture bath of a low boiling point solvent and water or a basic water bath liquid, etc. can also be used. Further, surfactants, anti-fogging agents 4], refractory metal salts, complex-forming compounds, etc. may be impregnated in the solvent.

These solvents can be used in dye-fixing materials, photosensitive materials, and in methods for applying them to both. The amount used is as small as a layer of solvent equivalent to the maximum swelling volume of the entire coating film - or less (especially less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film) ↓
Yes.

Rura may be applied to a solvent (for example, water) between the photosensitive layer of the heat-developable photosensitive material and the dye fixing layer of the dye fixing material to promote image formation and/or movement of the 7tμ color cord. It can also be used by incorporating it into the photosensitive layer, the dye fixing material, or both.

As a method of applying a solvent to the photosensitive layer or the dye fixing layer, Shio Riba et al.
There is a method described in line 4 on page 102.

In order to promote dye transfer, a method can also be adopted in which a hydrophilic thermal agent that is solid at room temperature and dissolves at high temperature is incorporated into the light-sensitive material or dye fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other polychoreds.

For the heating means in the transfer process,
6, page 102, line 14 to page 103, line 11. Alternatively, a layer of a conductive material such as graphite, carbon blank, metal, etc. may be applied to the dye fixing material, and an electric current may be passed through this tetraelectric layer to directly heat the dye.

A method for changing the pressure conditions and pressure when superimposing a heat-developable photosensitive material and a dye-fixing material and bringing them into close contact with each other Patent Application 1987-
The method described in No. 268926 (L+ 03-1o, s.) can be applied.

Hereinafter, examples of the present invention will be shown, and the present invention will be explained in more detail.
Congratulations.

Implementation Ij1 This article describes how to make benzotriazole silver emulsion.

Gelatin 28? and benzotriazole 1S2? water 30
@ Solve to 0mj and then. This solution was kept at 40°C and stirred.

Silver nitrate 17 in this solution? 2. Fermented 100dK of water with 2
Please add it in a minute.

The pH of this benzotriazole silver emulsion was adjusted, sedimentation was performed, and excess salt was removed. Thereafter, the pH was adjusted to &50 to obtain a benzotriazole silver emulsion with a yield of 400.

The ability to make silver halide emulsions for the 5th and 11th layers will be explained.

A well-stirred aqueous gelatin solution (containing 202 g of gelatin and 3 t of sodium chloride in 1,000 g of water, kept at 75°C) is mixed with 600 ml of an aqueous solution containing 295 moles each of sodium chloride and potassium bromide, and silver nitrate. A water bath solution (prepared by dissolving 59 mol of silver nitrate α in 600 ml of water) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol %) with an average grain size CL of 40 μm was prepared.

After washing with water and desalting, 5 ml of sodium thiosulfate and 20 q (i) of 4-hydroxy-6-methyl-1,5,3a,7-titrazaindene were added to carry out chemical sensitization at 60°C.

The emulsion yield was 6001.

Next, we will explain how to prepare a silver halide emulsion for the third layer.

Gelatin water mg, well stirred, <20r gelatin and chloride in water 1000mg) IJum 3? including 75
An aqueous solution containing 1295 moles each of IJium and potassium bromide with τ 600-
and a silver nitrate aqueous solution (59 moles of silver nitrate α dissolved in 600 d of water) were simultaneously added at equal flow rates through a hole for 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 135 μm was prepared.

After washing with water and desalting, 5η of sodium thiosulfate and 20 μ of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to carry out chemical sensitization at 60°C.

The yield of emulsion was 6001.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

The following yellow dye-donating product (YJ: 5?, succinic acid-2-ethyl-hexyl ester sulfonic acid sodium [15F] as a surfactant, triisononyl phosphate (2.5 lrff) as a high boiling point M medium, acetic acid ether 50
d was added and dissolved by heating at about 60° C. to form a homogeneous solution. After stirring and mixing this solution and lime-treated gelatin solution 1002, 110
Dispersed with 000rp VC. This dispersion is called a dispersion of a GK yellow coloration-donating substance.

The following magenta dye-providing substance (M) and cyan dye-providing substance! Dispersions of magenta and cyan dye-donating substances are prepared in exactly the same manner as in Step 9 of preparing dispersions of yellow dye-donating substances, except that (0) is used respectively.

Using these materials, a color photosensitive material having a multilayer structure as shown in Table 1 was prepared.

(Y) (MJ (CNOOH 8o20 H3 (D-i) CtH5021i5 (D-2 N (D-5) K Et 10 Used in Table-1; Encyclopedia is as per Table-2 It is.

Table-2 Next, we will discuss how to make the dye fixing material.

Laminate the following cloth on the paper support by laminating it with polyethylene-3
A dye fixing material coated with the following composition was made.

Table 3 I1) 1,2-bis(vinylsulfonylacetamide urethane) A tungsten light bulb was used in the above multilayered color photosensitive material, and a G, R1 and R three-color separation filter (G151ju) with continuously changing density was used. ~600nm.

The film was exposed to light at 500 lux for 1 second through an R of 600 to 700 nm (constructed using a filter that transmits R of 700 nm or more).

The emulsion surface of this exposed light-sensitive material is 20 ml/m
Water from step 2 was supplied using a wire bar, and then the dye fixing material and the membrane surface were overlapped so that they were in contact with each other. After heating for 60 seconds using a heat roller whose temperature was adjusted so that the temperature of fcta becomes 90 after absorbing water, the dye fixing material is peeled off from the photosensitive material, and a three-color separation filter of G, R1 and R is formed on the fixing material. Correspondingly, clear images of yellow, magenta, and cyan were obtained. Maximum degree (Dma:c) and minimum density (Dmin) of each color e Macbeth reflection densitometer (RD-519)
) was used to determine l1111. The results are shown in Table-4.

′! ! The photosensitive material was aged at 50° C. for one week, and then exposed and heated in the same manner as above.

The minimum concentration at that time is shown in Table 4.

The above results showed that the compound of the present invention has excellent stability over time of photosensitive materials. In other words, the compound of the present invention has almost the same minimum density as the comparative developer when used on a fresh photosensitive material, but the minimum density increases ( In other words, the compound of the present invention was shown to be extremely superior to the comparative developer in terms of increase in fog over time.

Example 2 5001497m'' of guanidine 4-acetylaminophenylpropiolate as a base breaker in the first layer
, 600 y+g/m2 in the second layer, 450 mg in the third layer
/m2, 600 mg/m2 in the 4th layer, 500 mg/m2 in the 5th layer
Photographic materials B-1 to B- were prepared in exactly the same manner as in Example 1, except that 600 mg/m2 was used in the sixth layer and the basic carbonate salt was used in the 2.4.6 layer. I made 6.

The dye-fixing material was prepared in exactly the same manner as in Example 1 except for guanidine picolinate. The sand was heated between two layers on a heat block heated to ℃.

20 ml/m2 of water on the surface where the dye fixing material is applied.
The film was supplied using a wire bar, and then the film was stacked so that the film surface was in contact with the photosensitive material heated above, and heated for 10 seconds using a heat roller at 90°C. When the dye-fixing material was peeled off from the gold-sensitive material, an image corresponding to the three-color separation filter was obtained on the dye-fixing material.

As in Example 1, the maximum of fresh photosensitive material, J1
The minimum density and minimum density of the light-sensitive materials were measured after aging at 50°C for one week, and the results are shown in Table 5.

In this example, as in Example 1, images with better minimum density stability were obtained using the compound of the present invention. 1 Example 3 The preparation of a hexahedral monodispersed silver iodobromide emulsion will be described.

A well-stirred gelatin aqueous solution (gelatin 202 and HO (CH2J2S (CH2)zB
(CH2)tO)1α5? Potassium bromide 69? and an aqueous solution containing 2t of potassium iodide and a silver nitrate aqueous solution (silver nitrate α in 600ml of water)
(dissolved 59 mol) by the double dient method
Keep it at g a D and add it. After washing with water and desalting, 40? of gelatin and water were added to adjust the pH, and optimal chemical sensitization was carried out using sodium thiosulfate to obtain hexahedral monodispersed emulsion 7005' with an average grain size α of 45 μm.

Next, we will discuss how to make a dispersion of dye-forming couplers.

100 tons of 10% aqueous gelatin solution, 107 tons of 5% aqueous solution of sodium dodenlebenzenesulfonate! , the dye-forming coupler M O, [:l 14 mol, trinonyl phosphate 5y, ethyl acetate 20 fLt?, described below. The mixture was mixed and emulsified dispersion 2 was prepared using a homogenizer.

Next, we will discuss how to prepare the coating liquid.

a) Hexahedral monodispersed silver iodobromide emulsion 50Pb) 1
0% gelatin aqueous solution 15yC) α04% methanol solution of sensitizing dye S with the following structure 5a11
! d) Dispersion of dye-forming coupler M 32 yθ) 10% methanol solution of compound t with the following structure 15-f 5% aqueous solution of the compound with the following structure 15- g) Water 168- Stir the above a) ~ After mixing, the mixture was coated onto a paper support laminated with polyethylene to a wet film thickness of 30 μm and dried.

Structure of sensitizing dye S Dye-forming power Structure of GRA-M Furthermore, as a protective layer, 10% gelatin bath solution 400? , 1,600 d of water, 1,2-bis(vinylsulfonylacetamidobuethane 4% aqueous F2L 20 g L1., succinic acid-2-ethylhexyl ester sulfonic acid), IJum salt 1% water @ 250 d of solution. Apply and dry until the liquid thickness is 42 μm, photosensitive material C-1
made.

Compound 1 of the present invention was used in place of the developer of θf in cL08.
The photosensitive material was prepared in exactly the same manner as 1C-1 except that 4 moles were used.
I made -2.

The photosensitive materials C-1 and C-22 were exposed to light for 1 second at 5000 lux using a tungsten bulb through a continuously changing density filter. 14-7 m2 of a 5% aqueous solution of guanidine carbonate was supplied to the emulsion surface of the exposed photosensitive material using a wire bar, and the polyethylene terephthalate film was stopped and heated at 9D DEG C. for 10 seconds. As a result, a clear magenta image is printed on the photosensitive material.
Liao was obtained.

After aging this light-sensitive material at 500℃ for 4 days, it was exposed and developed in the same way as above.The C-1 sample had a minimum density of 15, whereas the C-2 sample of the present invention had a minimum density of Cl3. It was shown that the temperature was stable over time without exceeding f'.

Example 4 The method for preparing a hexahedral monodisperse silver iodobromide emulsion will be described.

Gelatin water bath i (gelatin 202 and HO (CHJ! 5 (CH Ri, 5 (C4J)
,0HCL5? (and kept warm at 50℃ after devomiting)
Potassium bromide 69? and potassium iodide 2? An aqueous solution containing pAg F!
-0 and added. After washing with water and desalting, 40? of gelatin and 200 W 1 t of water to adjust the pH, perform optimal chemical sensitization using sodium thiosulfate, and reduce the average particle size α.
45μ hexahedral single-portion milk 700? I got it.

Next, we will discuss how to make a dispersion of the pigment-forming fuller.

10% gelatin in water 1100s', dodecylbenzenesulfone) IJum's 5% water fd # '''
z Mix 14 moles of the pigment-forming Dara Dα described below, 5 r of trinonyl phosphate, and 20 d of ethyl acetate,
An emulsified dispersion was made using a homogenizer.

Next, we will discuss how to prepare the coating solution.

a) Hexahedral monodispersed silver iodobromide emulsion 50 fb) 1
0% gelatin aqueous solution 15? C) Sensitized color ao a% metal solution with the following structure
5-d) Dispersion of dye-forming coupler D
52fe) Compound of the following structure t 0 10% methanol solution 15-f) 5% water bath solution of the compound of the following structure 151゜gJ 5-
Acetylamino-4-methquinphenyl-10 biol? 77 Nijin α70y
h) Water 168- After stirring and mixing the above a) to h), it was coated on a polyethylene terephthalate support to a wet film thickness of 75 μm and dried.

Structure of sensitizing dye Structure of dye-forming coupler D Furthermore, as a protective layer, 10% gelatin water-soluble g400? , water + 6oo, g, 1,2-bis(vinylsulfonylacetamido)ethane 4% water bath solution 2O+V, succinic acid-2-
Ethylhexyl ester sulfonic acid (ethylhexyl ester sulfonic acid) A liquid mixed with 250ml of 1% water bath solution of IJium salt.The wet liquid thickness is 42.
The photosensitive material D-1 was prepared by coating to a thickness of .mu.m.

Photosensitive material D-2 was prepared in exactly the same manner as photosensitive material D-1 except that 1084 moles of Compound 1 of the present invention was used in place of the developing agent in e).

The photosensitive materials D-1 and D-2 were exposed to light for 1 second at 5 [100 lux] using a tungsten bulb through a green filter whose degree of a was continuously changed. The exposed photosensitive material was heated for 60 seconds on a hot plate heated to 170° C., and then the applied emulsion layer was physically peeled off. A magenta color image was obtained on the polyethylene terephthalate. Macbeth transparent: Maximum density and minimum m degree are determined by 6mm II using IM density resistance TD-504. Results (!: Shown in Cloth-6.

Table 6' Also, after the unexposed light-sensitive material was incubated at 50°C for 7 days, it was exposed and heated in the same manner as above, and the minimum density was achieved in D-1 and D-2 of the present invention. I don't see any noticeable difference in food. The results measured with Macbeth transmission densitometer TD-504 are shown in Table 7 below.

Table-7 D-2 Compound 1 (present invention) 1. I Q, 1
The results of 0 or more indicate that the compound of the present invention provides a stable overall image.

(Effect of the invention) According to the present invention, it has excellent storage stability, has a high concentration of 8/8
Heat-developable color photosensitive materials that produce images with a high N ratio are the best.
t″L hole.

(2 others) %-1+, Ko

Claims (1)

[Scope of Claims] A heat-sensitive material containing at least a photosensitive silver halide, a coupler that binds to an oxidized developer, a hydrophilic binder, and at least one compound represented by the following general formula [Z] on a support. An image forming method characterized by heating a color photosensitive material to be developed in the presence of a base or a base generator. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Z] [In the formula, R_1, R_2, R_3 and R_4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, a hydroxyl group,
Amino group, substituted amino group, alkoxy group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acyl group, acyloxy group or alkoxycarbonyl group In this expression, R_1 and R_2 or R_3 and R_4 may be connected to form a ring. A is a hydroxyl group, a group that provides a hydroxyl group by the action of a nucleophile, or a ▲ mathematical formula, chemical formula, table, etc. ▼ group (R_6
, R_7 represents a hydrogen atom, an unsubstituted or substituted alkyl, alkenyl, cycloalkyl, or aralkyl group, and R_6 and R_7 may be linked to form a heterocycle). Also, if A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
One or both sets of (R_1 and R_6) and (R_3 and R_7) may be connected to form a heterocycle. R_5 represents a cyano group, an unsubstituted or substituted alkylsulfonyl group, or an arylsulfonyl group.